N,N-disubstituted hydroxylamine esters of substituted pyridyloxyphenoxypropionic acids and herbicidal methods of use

ABSTRACT

A herbicidal composition comprising an N,N-disubstituted hydroxylamine ester of a substituted pyridyloxyphenoxypropionic acid, and an inert diluent carrier, plus method of use.

This is a continuation of application Ser. No. 484,819, filed Apr. 13, 1983, abandoned.

BACKGROUND OF THE INVENTION

The present invention relates to certain hydroxylamine esters of substituted pyridyloxyphenoxy propionic acids which are particularly useful as post-emergent herbicides against annual and perennial grasses.

Herbicides are widely used by farmers, commercial agricultural companies, and other industries in order to increase crop yields for such staple crops as corn, soybeans, rice, and the like, and to eliminate weed growth along highways, railroad rights-of-way, and other areas. Herbicides are effective in killing or controlling unwanted weeds which compete for soil nutrients with the crop plants, and by reason of the fact that they kill weeds, are responsible for improving the aesthetic appearance of highway and railroad rights-of-way.

There are a number of different types of herbicides presently sold commercially, and these fall into two general categories. The categories are pre-emergence and post-emergence herbicides. The pre-emergence herbicides are normally incorporated into or applied to the soil prior to the emergence of the weed plants from the soil, and the post-emergence herbicides are normally applied to plant surfaces after emergence of the weeds or other unwanted plants from the soil.

THE PRIOR ART

The prior art is replete with examples of propionic acid-type compounds which have been disclosed to be herbicidally effective against grasses in particular, as compared to broad leaf weed pests. Examples of such prior art references include U.S. Pat. No. 4,200,587 and No. 4,325,729, both of which disclose propionic acid derivatives as being effective herbicides against grasses.

Efforts are constantly being made, however, to find compounds which are equal to or greater in effectiveness than presently existing compounds, or which are more economical to produce.

DESCRIPTION OF THE INVENTION

It has now been discovered that certain new and novel N,N-disubstituted hydroxylamine esters of substituted pyridyloxyphenoxy propionic acids have good herbicidal and plant growth regulating activity, particularly when applied as post-emergent herbicides and used against annual and perennial grasses.

As used herein, the term "herbicide" means a compound or composition which controls or modifies the growth of plants. By the term "herbicidally effective amount" is meant any amount of such compound or composition which causes a modifying effect upon the growth of plants. By "plants" is meant germinant seeds, emerging seedlings and established vegetation, including roots and above-ground portions. Such controlling or modifying effects include all deviations from natural development, such as killing, retardation, defoliation, desiccation, regulation, stunting, tillering, leaf burn, dwarfing and the like.

The new and novel compounds of this invention are N,N-disubstituted hydroxylamine esters of substituted pyridyloxyphenoxy propionic acids.

Of these hydroxylamine esters, certain ones are preferred. The preferred compounds have the formula ##STR1## wherein X is hydrogen or chlorine and Z is ##STR2## wherein R₁ and R₂ are the same or different and are straight or branched chain lower alkyl groups having from 1 to 6 carbon atoms, and n ranges from 4 to 7.

Representative compounds falling within the scope of the formula as set forth above include: 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]-propionic acid N-hydroxypiperdine ester, 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]-propionic acid, N,N-diethyl hydroxylamine ester, 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]-propionic acid N,N-dimethyl hydroxylamine ester, 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propionic acid N-hydroxypiperidine ester, 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propionic acid N,N-diethyl hydroxylamine ester, 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propionic acid N,N-dimethylhydroxylamine ester, 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]-propionic acid N-hydroxyhexamethyleneimine ester, 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propionic acid N-hydroxyhexamethyleneimine ester, and 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]-propionic acid N-ethyl,N-methylhydroxylamine ester.

The most preferred compounds for use in the practice of the invention include 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]propionic acid N,N-diethylhydroxylamine ester, 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]-propionic acid N,N-dimethylhydroxylamine ester, 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propionic acid N,N-diethylhydroxylamine ester, and 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propionic acid N,N-dimethylhydroxylamine ester.

The preferred compounds, as set forth above, have been found to have especially good herbicidal activity against perennial and annual grasses when applied as post-emergent herbicides. They are also effective as pre-emergent herbicides and plant growth regulators, but not to the same extent as when applied post-emergent.

The compounds of the invention can be produced in a multi-step process in accordance with the following generalized sequence of steps. ##STR3## where X and Z are as previously defined.

The end product compounds can be produced by selecting any one of the compounds produced in accordance with steps 1, 2, 3 or 4 above and continuing the reaction sequence as indicated.

Examples 1-4 below illustrate various methods of making the compounds of the invention using various starting materials.

EXAMPLE 1 Preparation of 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]-propionic acid, N,N-diethylhydroxylamine ester

A suitable 100 milliliter round bottom reaction flask was obtained, and into this flask was charged 2 grams (5.5 millimoles) of 2-(4-[5-trifluoromethyl-3-chloro-2-pyridyloxy]-phenoxy)-propionic acid along with 20 ml methylene chloride and four or five drops of dimethyl formamide. To this was added 1 ml. (11.5 millimole) of oxalyl chloride, dropwise. The contents of the flask were stirred for approximately one hour, then heated for one hour at reflux to produce 2.10 grams (5.5 millimoles) of the corresponding propionyl chloride.

The propionyl chloride was thereafter separated by conventional evaporation techniques. To the residual propionyl chloride was then added 0.49 grams (0.57 milliliters) of diethylhydroxylamine, and a solvent system of 0.45 ml pyridine and 25 ml of methylene chloride at ice bath temperature. The solution was then stirred overnight, and thereafter a mixture of hexane and water was added to the flask. The reactants were transferred to a separator funnel and washed sequentially with one molar hydrochloric acid, 5% sodium hydroxide, and brine, then dried over magnesium sulfate. The solvents were then evaporated off to yield 1.85 grams of product, which was purified by placing it in a silica column and then eluted with a 4:1 mixture of hexane and ethylacetate, followed by ethyl acetate. The subject compound was identified as such by conventional analytical techniques.

EXAMPLE 2 Preparation of 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]propionic acid, N-hydroxypiperidine ester

To a round bottom flask was charged 1.9 grams (5 millimole) of of 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]-propionyl chloride dissolved in 20 ml of methylene chloride under nitrogen, plus 0.5 ml (6.3 millimole) of pyridine. The solution was cooled in an ice bath, and to this was added 600 mg (6.7 millimole) of N-hydroxypiperidine dissolved in 5 ml methylene chloride. The reaction was complete after the addition of the amine was completed, and the reactants were further stirred for 5 minutes at 0° C., then 10 minutes at room temperature. The reactants were thereafter poured into water and washed sequentially with one molar hydrochloric acid, followed by water and brine, then dried over magnesium sulfate, yielding 1.6 grams of the subject compound which was identified as such by conventional analytical techniques.

EXAMPLE 3 Preparation of 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]-propionic acid, N,N-dimethylhydroxylamine ester

A round bottom flask was obtained and to this was added 7.4 grams (20 millimole) of 2-(4-[5-trifluoromethyl-3-chloro-2-pyridyloxy]-phenoxy) propionic acid slurried in 20 ml of ether under a nitrogen atmosphere. Thereafter 5 ml (68 millimoles) of thionyl chloride was added thereto, dropwise. The reactants were heated to reflux temperature and maintained at reflux for approximately 11/2 hours. The reactants were then stirred overnight at room temperature and concentrated on a rotovac, yielding 7.6 grams of the corresponding propionyl chloride. Thereafter 1.9 grams (5 millimole) of 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]-propionyl chloride was mixed with 600 mg (6.8 millimole) of N,N-diethylhydroxylamine and cooled in an ice bath. To this was added 0.50 ml (6.2 millimole) of pyridine and 5 ml of methylene chloride, all under a nitrogen atmosphere. The solution was stirred at 0° C. for approximately 75 minutes, then stirred at room temperature for one hour. The reactants were then poured into water, and washed with one molar hydrochloric acid, followed by water, and brine, and then dried over magnesium sulfate, yielding 1.6 grams of an oil identified by conventional analytical techniques as being the subject compound.

EXAMPLE 4 Preparation of 2-(4-[5-trifluoromethyl-2-pyridyloxy]-phenoxy)-propionic acid, N,N-diethyl hydroxylamine ester

A round bottom flask was obtained and into this flask was charged 5 grams (0.0275 moles) of 2-chloro-5-trifluoromethylpyridine and 5.4 grams of the methyl 2-(4-hydroxyphenoxy) propionate plus 5.7 grams potasium carbonate and 25 ml of acetonitrile solvent, and the solution was heated to reflux and refluxed for 22 hours. The product, the methyl ester of 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propionic acid was diluted with ether, filtered, and subjected to rotary vacuum to yield 7.65 grams of product. Thereafter, 6.6 grams of this product was mixed with 0.95 grams of sodium hydroxide along with a solvent system consisting of 10 ml water and 50 ml methanol. The reactants were heated for 15 minutes after which the methanol was vacuumed off and water was added and extracted with ether. The water layer was then acidified with hydrochloric acid and the product extracted into ether, washed with brine, and dried over magnesium sulfate, then rotary vacuumed to drive off the ether, yielding 4.7 grams 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]propionic acid.

The propionic acid was then processed in accordance with the procedure described in Example 2 which yielded a quantity of the end product, 2-(4-[5-trifluoromethyl-2-pyridyloxy]-phenoxy)-propionic acid, N,N,-diethylhydroxylamine ester.

Similar techniques can be used to produce the other compounds of the invention, by varying the starting material in order to achieve the desired end products.

The pyridine compound shown above as being the initial starting compound in accordance with the process for producing the compounds of the invention, is described in U.S. Pat. No. 4,184,041. The second compound, the phenol, is described and claimed in U.S. Pat. No. 4,152,328. The third compound, the propionic acid, is described and claimed in U.S. Pat. No. 4,325,729, while the fourth compound, the propionyl chloride, is described in U.S. Pat. No. 4,317,913. Each of these patents disclose methods of producing each of the intermediate compounds which themselves can be used in the process for producing the end product compounds of this invention.

The herbicidal activity of representative ones of the compounds of the invention as exhibited by means of tests in accordance with the following procedure.

EXAMPLE 5 HERBICIDAL ACTIVITY TESTS

This example offers herbicidal activity test data to show the effectiveness of the compounds of the invention. The effect is observed by comparing the extent of weed control in test flats treated with the hydroxylamine esters against that occurring in similar control flats. The soil used in these tests was a sandy loam soil from the Livermore, Cal. area.

Also added to the soil was 17-17-17 fertilizer (N-P₂ O₅ -K₂ O weight basis), a mounting to 50 ppm by weight with respect to the soil, and 100 ppm Captan, a soil fungicide.

The treated soil was then placed in flats which were 3 inches deep, 6 inches wide, and 10 inches long. The soil was tamped and leveled with a row marker to impress six rows across the width of the flat. The test weeds were as follows:

    ______________________________________                                         COMMON NAME         SCIENTIFIC NAME                                            ______________________________________                                         Grasses                                                                        A. shattercane (SHC)                                                                               Sorgum bicolor                                             B. annual ryegrass (ARG)                                                                           Lolium multiflorum                                         C. watergrass (WG)  Echinochloa crusgalli                                      D. wild oat (WO)    Avena fatua                                                E. green foxtail (GFT)                                                                             Setaria viridis                                            ______________________________________                                    

Sufficient seeds were planted to produce several seedlings per inch in each row. The flats were then placed in a greenhouse maintained at 70° to 85° F. (21° to 30° C.) and the plant stems were watered daily by sprinkler.

Chemical application is made by spraying 10 days after planting. The spray solution is prepared by dissolving 48 mg of herbicide compound in 20 ml of acetone containing 1% Tween® 20 (polyoxysorbitan monolaurate), then adding 20 ml of water to the resulting solution. The solution is sprayed at 25 gallons/acre, resulting in a 1/4 lb/acre rate of chemical application. Other rates were achieved by varying the solution concentration and/or the rate of spray.

Approximately 12-14 days after treatment, the degree of weed control was estimated and recorded as percentage control compared to the growth of the same species in an untreated check flat of the same age. The rating scale ranges from 0 to 100%, where 0 equals no effect with plant growth equal to the untreated control, and 100 equals complete kill.

The results are listed in Tables I and II below. It is clear from the results shown in these tables that the compounds of this invention are effective herbicides, particularly against annual and perennial grasses.

                  TABLE I                                                          ______________________________________                                         HERBICIDE TEST RESULTS                                                                    Appli-                                                                         cation                                                                               Percent Control                                                          Rate  Grasses                                                       TEST COMPOUND                                                                               (lb/A)  WG     SHC  GFT  WO   AVE                                 ______________________________________                                         1. 2-[4-(5-trifluoro-                                                                       1/32    60     65   20   20   44                                  methyl-2-pyridyloxy)-                                                                               65     70   20   30                                       phenoxy]-propionic                                                                          1/16    90     95   20   30   63                                  acid N,N--diethyl-   85     95   50   40                                       hydroxylamine ester                                                                         1/8     85     95   50   40   69                                                       90     98   40   55                                                    1/4     100    98   80   90   88                                                       95     98   80   60                                       2. 2-[4-(5-trifluoro-                                                                       1/32    30     60   20    0   28                                  methyl-2-pyridyloxy)-                                                                               40     60   10   49                                       phenoxy]-propionic                                                                          1/16    75     85   10   10   49                                  acid N--hydroxy-     75     90   20   30                                       piperidine ester                                                                            1/8     95     98   65   65   73                                                       85     95   40   40                                                    1/4     98     98   60   60   82                                                       98     100  70   70                                       3. 2-[4-(5-trifluoro-                                                                       1/32    95     98   70   50   78                                  methyl-3-chloro-2-   95     98   60   60                                       pyridyloxy)-phenoxy]-                                                                       1/16    100    100  85   70   86                                  propionic acid N,N-- 100    100  85   50                                       diethylhydroxylamine                                                                        1/8     100    100  98   95   98                                  ester                100    100  98   90                                                    1/4     100    100  100  98   100                                                      100    100  100  98                                       4. Control            0      0    0    0    0                                  ______________________________________                                          AVE = The average of all replications at a given application rate.       

                  TABLE II                                                         ______________________________________                                         HERBICIDE TEST RESULTS                                                                     Appli-                                                                         cation  Percent Control                                            TEST        Rate    Grasses                                                    COMPOUND    (lb/A)  WG     WO   GFT  ARG   AVE                                 ______________________________________                                         1. 2-[4-(5-trifluoro-                                                                      1/32     70    40   40   10    40                                  methyl-3-chloro-2-   95    70   70   60    74                                  pyridyloxy)-phen-                                                                          1/16     98    80   75   70    81                                  oxy]-propionic acid 100    75   75   30    70                                  N--hydroxypiper-                                                                           1/8     100    75   65   60    75                                  idine ester         100    90   90   90    93                                              1/4     100    98   98   90    97                                                      100    98   98   80    94                                  2. 2-[4-(5-trifluoro-                                                                      1/32     75    70   50   60    64                                  methyl-3-chloro-2-   98    75   70   60    76                                  pyridyloxy)-phen-                                                                          1/16    100    95   90   80    92                                  oxy]-propionic acid  95    80   75   80    83                                  N,N--diethylhy-                                                                            1/8     100    90   85   75    89                                  droxylamine ester   100    95   98   95    88                                              1/4     100    99   100  99    100                                                     100    98   98   95    98                                  ______________________________________                                    

METHODS OF APPLICATION

The herbicidal compositions of the present invention are useful in controlling the growth of undesirable vegetation by pre-emergence or post-emergence application to the locus where control is desired, including pre-plant and post-plant soil incorporation as well as surface application. The compositions are generally embodied in formulations suitable for convenient application. Typical formulations contain additional ingredients or diluent carriers which are either inert or active. Examples of such ingredients or carriers are water, organic solvents, dust carriers, granular carriers, surface active agents, oil and water, water-oil emulsions, wetting agents, dispersing agents, and emulsifying agents. The herbicidal formulations generally take the form of dusts, emulsifiable concentrates, granules and pellets, or microcapsules.

A. DUSTS

Dusts are dense powder compositions which are intended for application in dry form. Dusts are characterized by their free-flowing and rapid settling properties so that they are not readily windborne to areas where their presence is not desired. They contain primarily an active material and a dense, free-flowing, solid carrier.

Their performance is sometimes aided by the inclusion of a wetting agent, and convenience in manufacture frequently demands the inclusion of an inert, absorptive grinding aid. For the dust compositions of this invention, the inert carrier may be either of vegetable or mineral origin, the wetting agent is preferably anionic or nonionic, and suitable absorptive grinding aids are of mineral origin.

Suitable classes of inert solid carriers for use in the dust compositions are those organic or inorganic powders which possess high bulk density and are very free-flowing. They are also characterized by low surface area and poor liquid absorptivity. Suitable grinding aids are natural clays, diatomaceous earths, and synthetic mineral fillers derived from silica or silicate. Among ionic and nonionic wetting agents, the most suitable are the members of the group known to the art as wetting agents and emulsifiers. Although solid agents are preferred because of ease of incorporation, some liquid nonionic agents are also suitable in the dust formulations.

Preferred dust carriers are micaceous talcs, pyrophyllite, dense kaolin clays, tobacco dust and ground calcium phosphate rock.

Preferred grinding aids are attapulgite clay, diatomaceous silica, synthetic fine silica and synthetic calcium and magnesium silicates.

Most preferred wetting agents are alkylbenzene and alkyl-naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, and ditertiary acetylenic glycols. Preferred dispersants are methyl cellulose, polyvinyl alcohol, lignin sulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalenesulfonate, polymethylene bisnaphthalenesulfonate, and sodium-N-methyl-N-(long chain acid) taurates.

The inert solid carriers in the dusts of this invention are usually present in concentrations of from about 30 to 90 weight percent of the total composition. The grinding aid will usually constitute 5 to 50 weight percent of the compositions, and the wetting agent will constitute from about 0 to 1.0 weight percent of the composition. Dust compositions can also contain other surfactants such as dispersing agents in concentrations of up to about 0.5 weight percent, and minor agents of anticaking and antistatic agents. The particle size of the carrier is usually in the range of 30 to 50 microns.

B. EMULSIFIABLE CONCENTRATES

Emulsifiable concentrates are usually solutions of the active materials in nonwater-miscible solvents together with an emulsifying agent. Prior to use, the concentrate is diluted with water to form a suspended emulsion of solvent droplets.

Typical solvents for use in emulsifiable concentrates include weed oils, chlorinated hydrocarbons, and nonwater-miscible ethers, esters, and ketones.

Typical emulsifying agents are anionic or nonionic surfactants, or mixtures of the two. Examples include long-chain alkyl or mercaptan polyethoxy alcohols, alkylaryl polyethoxy alcohols, sorbitan fatty acid esters, polyoxyethylene ethers with sorbitan fatty acid esters, polyoxyethylene glycol esters with fatty or rosin acids, fatty alkylol amide condensates, calcium and amine salts of fatty alcohol sulfates, oil soluble petroleum sulfonates, or preferably mixtures of these emulsifying agents. Such emulsifying agents will comprise from about 1 to 10 weight percent of the total composition.

Thus, emulsifiable concentrates of the present invention will consist of from about 15 to about 50 weight percent active material, about 40 to 82 weight percent solvent, and about 1 to 10 weight percent emulsifier. Other additives such as spreading agents and stickers can also be included.

C. GRANULES AND PELLETS

Granules and pellets are physically stable, particulate compositions containing the active ingredients adhering to or distributed through a basic matrix of a coherent, inert carrier with microscopic dimensions. A typical particle is about 1 to 2 millimeters in diameter. Surfactants are often present to aid in leaching of the active ingredient from the granule or pellet.

The carrier is preferably of mineral origin, and generally falls within one of two types. The first are porous, absorptive, preformed granules, such as preformed and screened granular attapulgite or heat expanded, granular, screened vermiculite. On either of these, a solution of the active agent can be sprayed and will be absorbed at concentrations up to 25 weight percent of the total weight. The second, which are also suitable for pellets, are initially powdered kaolin clays, hydrated attapulgite, or bentonite clays in the form of sodium, calcium, or magnesium bentonites. Water-soluble salts, such as sodium salts, may also be present to aid in the disintegration of granules or pellets in the presence of moisture. These ingredients are blended with the active components to give mixtures that are granulated or pelleted, followed by drying, to yield formulations with the active component distributed uniformly throughout the mass. Such granules and pellets can also be made with 25 to 30 weight percent active component, but more frequently a concentration of about 10 weight percent is desired for optimum distribution. The granular compositions of this invention are most useful in a size range of 15-30 mesh.

The surfactant is generally a common wetting agent of anionic or nonionic character. The most suitable wetting agents depend upon the type of granule used. When preformed granules are sprayed with active material in liquid form the most suitable wetting agents are nonionic, liquid wetters miscible with the solvent. These are compounds most generally known in the art as emulsifiers, and comprise alkylaryl polyether alcohols, alkyl polyether alcohols, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol esters with fatty or rosin acids, fatty alkylol amide condensates, oil solution petroleum or vegetable oil sulfonates, or mixtures of these. Such agents will usually comprise up to about 5 weight percent of the total composition.

When the active ingredient is first mixed with a powdered carrier and subsequently granulated, or pelleted, liquid nonionic wetters can still be used, but it is usually preferable to incorporate at the mixing stage one of the solid, powdered anionic wetting agents such as those previously listed for the wettable powders. Such agents will comprise from about 0 to 2 weight percent of the total composition.

Thus, the preferred granular or pelleted formulations of this invention comprise about 5 to 30 percent by weight active material, about 0 to 5 weight percent wetting agent, and about 65 to 95 weight percent inert material carrier, as these terms are used herein.

D. MICROCAPSULES

Microcapsules consist of fully enclosed droplets or granules containing the active materials, in which the enclosing material is an inert porous membrane, arranged to allow escape of the enclosed materials to the surrounding medium at controlled rates over a specified period. Encapsulated droplets are typically about 1 to 50 microns in diameter.

The enclosed liquid typically constitutes about 50 to 95% of the weight of the entire capsule, and may contain a small amount of solvent in addition to the active materials.

Encapsulated granules are characterized by porous membranes sealing the openings of the granule carrier pores, trapping the liquid containing the active components inside for controlled release. A typical granule size ranges from 1 millimeter to 1 centimeter in diameter. In agricultural useage, the granule size is generally about 1 to 2 ml in diameter. Granules formed by extrusion, agglomeration, or prilling are useful in the present invention as well as materials in their naturally occurring form. Examples of such carriers are vermiculite, sintered clay granules, kaolin, attapulgite clay, sawdust, and granular carbon.

Useful encapsulating materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyurethanes, and starch xanthates.

E. IN GENERAL

Each of the above formulations can be prepared as a package containing the herbicide together with the other ingredients of the formulation (diluents, emulsifiers, surfactants, etc.). The formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site.

In general, any conventional method of application can be used. The locus of application can be soil, seeds, seedlings, or the actual plants, as well as flooded fields. Post-emergent application is preferred. Dusts and liquid compositions can be applied by the use of powder dusters, boom and hand sprayers, and spray dusters. The compositions can also be applied from airplanes as dusts and sprays because they are effective in very low dosages. In order to modify or control the growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are distributed in the soil to a depth of at least one-half inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles. Instead, these compositions can be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

The herbicide compositions can also be applied to the soil through irrigation systems. According to this technique, the compositions are added directly to irrigation water immediately prior to irrigation of the field. This technique is applicable in all geographical areas regardless of rainfall, since it permits supplementation of the natural rainfall at critical stages of plant growth. In a typical application, the concentration of the herbicide composition in the irrigation water will range from about 10 to 150 parts per million by weight. The irrigation water can be applied by the use of sprinkler systems, surface furrows, or flooding. Such application is most effectively done before the weeds germinate, either early in the spring prior to germination or within two days after cultivation of the field.

The amount of the present composition which constitutes a herbicidally effective amount depends upon the nature of the seeds or plants to be controlled. The rate of application of active ingredient varies from about 0.01 to about 50 pounds per acre, preferably about 0.1 to about 25 pounds per acre with the actual amount depending on the overall cost and the desired results. It will be readily apparent to one skilled in the art that compositions exhibiting lower herbicidal activity will require a higher dosage than more active compounds for the same degree of control. 

What is claimed is:
 1. As new compounds, N,N-disubstituted hydroxylamine esters of substituted pyridyloxyphenoxy propionic acids having the formula ##STR4## wherein X is hydrogen or chlorine and Z is ##STR5## wherein R₁ and R₂ are the same or different and are straight or branched chain lower alkyl groups having from 1 to 6 carbon atoms, and n is 4 to
 6. 2. The compound of claim 1 in which X is Cl.
 3. The compound of claim 1 in which X is H.
 4. The compound of claim 1 or 2 in which Z is ##STR6## and R₁ and R₂ are each ethyl.
 5. The compound of claim 1 or 2 in which X is ##STR7## where n is
 5. 6. The compound of claim 1 in which Z is ##STR8## and R₁ and R₂ are each methyl.
 7. The compound of claim 1 in which Z is ##STR9## and n is
 6. 8. A herbicidal composition which comprises a herbicidally effective amount of an N,N-disubstituted hydroxylamine ester of substituted pyridyloxyphenoxypropionic acid having the formula ##STR10## wherein X is hydrogen or chlorine and X is ##STR11## wherein R₁ and R₂ are the same or different and are straight or branched chain lower alkyl groups having from 1 to 6 carbon atoms, and n is 4 to 6, and a diluent carrier.
 9. The composition method of claim 8 in which X is Cl.
 10. The composition of claim 8 in which X is H.
 11. The composition of claim 8 in which Z is ##STR12## where R₁ and R₂ are each ethyl.
 12. The composition of claim 8 in which Z is ##STR13## where R₁ and R₂ are each methyl.
 13. The composition of claim 8 in which Z is ##STR14## wherein n is 5 or
 6. 14. A method for controlling undesirable weed pests which comprises applying to the locus where control is desired a herbicidally effective amount of a compound having the formula ##STR15## wherein X is hydrogen or chlorine and Z is ##STR16## wherein R₁ and R₂ are the same or different and are straight or branched chain lower alkyl groups having from 1 to 6 carbon atoms, and n ranges from 4 to
 6. 15. The method of claim 14 in which X is Cl.
 16. The method of claim 14 in which X is H.
 17. The method of claim 14 in which Z is ##STR17## where R₁ and R₂ are each ethyl.
 18. The method of claim 14 in which Z is ##STR18## where R₁ an R₂ are each methyl.
 19. The method of claim 14 in which Z is ##STR19## wherein n is 5 or
 6. 20. A herbicidal composition comprising a herbicidally effective amount of a N,N-disubstituted hydroxylamine ester of a substituted pyridyloxyphenoxypropionic acid, and an inert diluent carrier.
 21. The composition of claim 20 in which said ester is 2-[4-(5-trifluoromethyl-3-chloro-2-pyridyloxy)-phenoxy]-propionic acid, N,N-diethyl hydroxylamine ester. 